High-temperature hydrogen as well as preparation method and application thereof

Abstract

The invention provides high-temperature hydrogen as well as a preparation method and application thereof, and belongs to the technical field of chemical production. The preparation method of the high-temperature hydrogen provided by the invention comprises the following steps: heating hydrogen by adopting a high-temperature carbon component to obtain the high-temperature hydrogen, and the temperature of the high-temperature carbon component is 1700-3000 DEG C. The high-melting-point carbon component is adopted and can be heated to the high temperature (1700-3000 DEG C), so that the hydrogen can be heated, and the hydrogen reaches the high temperature. Experimental results show that the temperature of the high-temperature hydrogen provided by the invention reaches 1500-2000 DEG C.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical production, and specifically relates to high-temperature hydrogen and a preparation method and application thereof. Background Art

[0002] Metal carbonates, such as calcium carbonate (CaCO3), magnesium carbonate (MgCO3) and dolomite (CaMg(CO3)2), are raw materials for important industrial fields such as cement, steel, refractory materials, and calcium carbide. These metal carbonates must first be converted into metal oxides before they can be used in subsequent production processes. Currently, the technology for converting metal carbonates into metal oxides is thermal decomposition, such as the thermal decomposition of calcium carbonate: CaCO3 = CaO + CO2.

[0003] At present, the industrial technology of thermal decomposition of metal carbonates uses an external resistance wire or electrode to heat the metal tube reactor, and then heats the material (metal carbonate and hydrogen) in the tube through the heat conduction of the tube wall. Due to the limitation of the melting point of the metal tube, the heating temperature is not high. Since the highest temperature of the whole system is the resistance wire outside the reactor, followed by the metal reactor, the heat dissipation of the system is large and the heating efficiency is low. There are also reports of methods of heating hydrogen with heat exchange media such as hot liquid or thermal oil, but the temperature of the hydrogen after heating is lower than 200 ° C. Subsequently, electromagnetic induction heating technology appeared, which uses metal to generate eddy currents in an alternating magnetic field to generate heat, is highly efficient and energy-saving, has a fast heating speed, and is simple to control. However, electromagnetic induction heats an iron furnace, and heats the hydrogen inside it through the heat conduction of iron. The metal tube wall is the highest temperature in the whole system, and the heat dissipation to the outside is large. Moreover, due to the melting point limitation of the iron material, it cannot be heated to a higher temperature, so high-temperature hydrogen cannot be obtained, and thus high-temperature hydrogen cannot be used as a reduction heat carrier and reducing agent for thermal decomposition of metal carbonates. Therefore, how to prepare high-temperature hydrogen has become a technical problem that needs to be solved in this field. Summary of the invention

[0004] The purpose of the present invention is to provide a high temperature hydrogen and its preparation method and application. The temperature of the high temperature hydrogen provided by the present invention reaches 1500-2000°C.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing high-temperature hydrogen, comprising:

[0007] High-temperature carbon components are used to heat hydrogen to obtain high-temperature hydrogen;

[0008] The temperature of the high temperature carbon component is 1700-3000°C.

[0009] Preferably, the material of the high temperature carbon component includes coke, needle coke or graphite.

[0010] Preferably, the high temperature carbon component is heated by electromagnetic induction heating.

[0011] Preferably, the concentration of the hydrogen is 50.0-99.9 vol%.

[0012] Preferably, the heating time is 0.01 to 1 s.

[0013] The present invention also provides high-temperature hydrogen prepared by the preparation method described in the above technical solution.

[0014] Preferably, the temperature of the high-temperature hydrogen is 1500-2000°C.

[0015] The present invention also provides the use of the high-temperature hydrogen described in the above technical solution as a reduction heat carrier and reducing agent for metal carbonates.

[0016] Preferably, the application of the high temperature hydrogen as a reduction heat carrier and reducing agent for the metal carbonate comprises:

[0017] The high temperature hydrogen is reacted with the metal carbonate to obtain metal oxides, carbon dioxide and carbon monoxide.

[0018] Preferably, the temperature of the hydrogenation reaction is 600-1500° C., and the time of the hydrogenation reaction is 1-15 min.

[0019] The present invention provides a method for preparing high-temperature hydrogen, comprising: heating hydrogen with a high-temperature carbon component to obtain high-temperature hydrogen; the temperature of the high-temperature carbon component is 1700-3000°C. The present invention uses a high-melting-point carbon component, which can be heated to a high temperature (1700-3000°C), so as to heat the hydrogen and make the hydrogen reach a high temperature. Experimental results show that the temperature of the high-temperature hydrogen provided by the present invention reaches 1500-2000°C. DETAILED DESCRIPTION

[0020] The present invention provides a method for preparing high-temperature hydrogen, comprising:

[0021] High-temperature carbon components are used to heat hydrogen to obtain high-temperature hydrogen.

[0022] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known in the art.

[0023] In the present invention, the temperature of the high temperature carbon component is 1700-3000° C., preferably 1700-2500° C., and more preferably 1800-2200° C. In the present invention, the temperature of the high temperature carbon component is limited within the above range to heat the hydrogen to a high temperature, thereby obtaining the required high temperature hydrogen, and no external heat source is required for the subsequent reduction of the metal carbonate.

[0024] As an embodiment, the temperature of the high temperature carbon component may be 2800°C, 2300°C or 2000°C.

[0025] In the present invention, the material of the high temperature carbon component preferably includes coke, needle coke or graphite, and more preferably graphite. The present invention has no special requirements on the shape of the carbon component, and it only needs to ensure that hydrogen can pass through. As an embodiment of the present invention, the shape of the carbon component can be tubular, rod-shaped and granular, and hydrogen can pass through the inside of the tube, outside of the tube, and the gaps of the rod or particles. As long as there is enough space for hydrogen to pass through, other forms will not be repeated.

[0026] In the present invention, the heating method of the high temperature carbon component is preferably electromagnetic induction heating; the frequency of the electromagnetic induction is preferably 20 to 1000 kHz, more preferably 100 to 800 kHz, and most preferably 300 to 500 kHz. The present invention has no special limitation on the time of the electromagnetic induction heating, as long as the temperature of the high temperature carbon component is within the range of 1700 to 3000°C.

[0027] In the present invention, the operation obtained by electromagnetic induction heating is preferably to arrange a carbon component in a device that does not shield a magnetic field, to arrange an induction coil outside the device, and to heat the carbon-based component in the device to a high temperature by electromagnetic induction.

[0028] In the present invention, the concentration of the hydrogen is preferably 50.0-99.9 vol%, more preferably 85.0-99.9 vol%, and most preferably 90.0-99.9 vol%; the flow rate of the hydrogen is preferably 0.5-10 m / s, more preferably 2-8 m / s, and most preferably 4-6 m / s.

[0029] In the present invention, the heating time is preferably 0.01 to 1 s, more preferably 0.01 to 0.8 s, and most preferably 0.01 to 0.4 s. The present invention limits the heating time to the above range, which can further ensure the high-temperature hydrogen.

[0030] As an implementation manner, the heating time may be 0.1s, 0.2s, 0.3s, 0.5s or 0.6s.

[0031] The present invention adopts a high melting point carbon component which can be heated to a high temperature (1700-3000° C.), thereby heating hydrogen to a high temperature.

[0032] The present invention also provides high-temperature hydrogen prepared by the preparation method described in the above technical solution.

[0033] In the present invention, the temperature of the high temperature hydrogen is preferably 1500-2000°C, more preferably 1700-1800°C.

[0034] The present invention also provides the use of the high-temperature hydrogen described in the above technical solution as a reduction heat carrier and reducing agent for metal carbonates.

[0035] In the present invention, the application of the high temperature hydrogen as a reduction heat carrier and reducing agent for metal carbonate preferably includes:

[0036] The high temperature hydrogen is reacted with the metal carbonate to obtain metal oxides, carbon dioxide and carbon monoxide.

[0037] In the present invention, the metal carbonate is preferably one or more of heavy calcium carbonate, light calcium carbonate, limestone powder, calcite, dolomite, heavy magnesium carbonate and light magnesium carbonate. When the metal carbonate is a plurality of the above, the present invention has no particular limitation on the ratio of the plurality of the above, and any ratio can be used.

[0038] In the present invention, the metal carbonate is preferably in powder or block form, more preferably in powder form; the particle size of the metal carbonate is preferably 0.1 to 10 mm, more preferably 0.1 to 5 mm, and most preferably 1 to 3 mm.

[0039] In the present invention, the ratio of the mass of the metal carbonate to the volume of the high-temperature hydrogen is preferably 1 g: (0.5-5) L, more preferably 1 g: (1-4) L, and most preferably 1 g: (2-3) L.

[0040] In the present invention, the hydrogenation reaction is preferably carried out in a reduction furnace; the high-temperature hydrogen is preferably sprayed into the reduction furnace for the hydrogenation reaction. In the present invention, the high-temperature hydrogen is used not only as a reducing agent but also as a heat source, so that no external heat source is required during the hydrogenation reaction, thereby reducing costs and investment.

[0041] In the present invention, the temperature of the hydrogenation reaction is preferably 600-1500°C, more preferably 700-1200°C, most preferably 800-1000°C; the time of the hydrogenation reaction is preferably 1-15 min, more preferably 1-10 min, most preferably 3-5 min.

[0042] As an embodiment, the temperature of the hydrogenation reaction may be 800° C., 900° C. or 1000° C.; the time of the hydrogenation reaction may be 3 min, 4 min, 5 min, 6 min, 7 min or 8 min.

[0043] The method provided by the present invention can realize the safe and efficient generation of metal oxides and carbon monoxide from metal carbonate in a hydrogen atmosphere, is suitable for the transformation of existing oxygen thermal decomposition devices, completely avoids carbon dioxide emissions, and can further utilize the generated gas.

[0044] The current industrial technology for producing metal oxides from metal carbonates relies on fuel combustion for heating. To transform this technology into hydrogen reduction, the heating method of in-situ oxidation combustion must be changed at the same time. The present invention heats carbon components through electromagnetic induction to prepare high-temperature hydrogen, which is then used as a heat source and hydrogen source for the metal carbonate hydrogenation reduction reaction, achieving technological innovation. Compared with technologies such as in-furnace combustion and indirect heating by resistance furnaces, the present invention has a simple process and can be used in existing industrial equipment without large-scale modifications. It has a high hydrogen temperature, a fast heating rate, and a short reaction time, making it suitable for large-scale production. The carbon monoxide produced can also be further used in the generation of other chemicals, with good economic efficiency.

[0045] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0046] The present invention uses the following formula to calculate the metal carbonate conversion rate:

[0047] Carbonate conversion rate = (molar amount of carbon monoxide + carbon dioxide produced) / molar amount of carbon in carbonate source × 100%;

[0048] Carbon monoxide conversion rate = (molar amount of carbon monoxide produced / molar amount of carbon in carbonate source) × 100%;

[0049] Carbon dioxide conversion rate = (molar amount of carbon dioxide produced / molar amount of carbon in carbonate source) × 100%.

[0050] Example 1

[0051] The method for preparing high temperature hydrogen is as follows:

[0052] (1) Induction heating the carbon component to 2300° C. in an alternating magnetic field at a frequency of 400 kHz to obtain a high-temperature carbon component; wherein the material of the high-temperature carbon component is graphite;

[0053] (2) Hydrogen with a concentration of 99.9 vol% and a flow rate of 8 m / s is heated to 1800°C by passing through a high-temperature carbon component for 0.5 s to obtain high-temperature hydrogen.

[0054] Application Example 1

[0055] The high-temperature hydrogen prepared in Example 1 was hydrogenated with light calcium carbonate with a particle size of 0.5 mm at 1000°C for 5 minutes. The ratio of the mass of light calcium carbonate to the volume of high-temperature hydrogen was 1g:4L. Solid product calcium oxide was obtained. The yield of carbon monoxide in the gas product was 90%, and the yield of carbon dioxide was 10%.

[0056] Example 2

[0057] The method for preparing high temperature hydrogen is as follows:

[0058] (1) Induction heating the carbon component to 3000° C. in an alternating magnetic field with a frequency of 1000 kHz to obtain a high-temperature carbon component; wherein the material of the high-temperature carbon component is graphite;

[0059] (2) Hydrogen with a concentration of 50 vol% and a flow rate of 0.5 m / s is heated to 2000°C by passing through a high-temperature carbon component for 0.1 s to obtain high-temperature hydrogen.

[0060] Application Example 2

[0061] The high-temperature hydrogen prepared in Example 2 was hydrogenated with heavy calcium carbonate with a particle size of 10 mm at 1500°C for 7 minutes. The ratio of the mass of heavy calcium carbonate to the volume of high-temperature hydrogen was 1g:0.5L. Solid product calcium oxide was obtained. The yield of carbon monoxide in the gas product was 75%, and the yield of carbon dioxide was 25%.

[0062] Example 3

[0063] The method for preparing high temperature hydrogen is as follows:

[0064] (1) induction heating the carbon component to 2300° C. in an alternating magnetic field with a frequency of 1000 kHz to obtain a high-temperature carbon component; wherein the material of the high-temperature carbon component is coke;

[0065] (2) Hydrogen with a concentration of 80 vol% and a flow rate of 10 m / s is heated to 1800°C by passing through a high-temperature carbon component for 0.5 s to obtain high-temperature hydrogen.

[0066] Application Example 3

[0067] The high-temperature hydrogen prepared in Example 3 was hydrogenated with light calcium carbonate with a particle size of 0.1 mm at 1000° C. for 3 min. The ratio of the mass of light calcium carbonate to the volume of high-temperature hydrogen was 1 g:5 L. Solid product calcium oxide was obtained. The yield of carbon monoxide in the gas product was 92%, and the yield of carbon dioxide was 8%.

[0068] Example 4

[0069] The method for preparing high temperature hydrogen is as follows:

[0070] (1) Induction heating the carbon component to 2000° C. in an alternating magnetic field at a frequency of 600 kHz to obtain a high-temperature carbon component; wherein the high-temperature carbon component is made of coke;

[0071] (2) Hydrogen with a concentration of 90 vol% and a flow rate of 3 m / s is heated to 1700°C by passing through a high-temperature carbon component for 0.1 s to obtain high-temperature hydrogen.

[0072] Application Example 4

[0073] The high-temperature hydrogen prepared in Example 4 was hydrogenated with light calcium carbonate with a particle size of 0.3 mm at 900°C for 4 minutes. The ratio of the mass of light calcium carbonate to the volume of high-temperature hydrogen was 1g:2L. Solid product calcium oxide was obtained. The yield of carbon monoxide in the gas product was 85%, and the yield of carbon dioxide was 15%.

[0074] Example 5

[0075] The method for preparing high temperature hydrogen is as follows:

[0076] (1) induction heating the carbon component to 1700° C. in an alternating magnetic field with a frequency of 20 kHz to obtain a high-temperature carbon component; wherein the material of the high-temperature carbon component is needle coke;

[0077] (2) Hydrogen with a concentration of 85 vol% and a flow rate of 5 m / s is heated to 1500°C by passing through a high-temperature carbon component for 0.2 s to obtain high-temperature hydrogen.

[0078] Application Example 5

[0079] The high-temperature hydrogen prepared in Example 5 was hydrogenated with light calcium carbonate with a particle size of 0.2 mm at 800°C for 6 minutes. The ratio of the mass of light calcium carbonate to the volume of high-temperature hydrogen was 1g:3L. Solid product calcium oxide was obtained. The yield of carbon monoxide in the gas product was 88%, and the yield of carbon dioxide was 12%.

[0080] Example 6

[0081] The method for preparing high temperature hydrogen is as follows:

[0082] (1) Induction heating the carbon component to 2000° C. in an alternating magnetic field with a frequency of 100 kHz to obtain a high-temperature carbon component; wherein the material of the high-temperature carbon component is graphite;

[0083] (2) Hydrogen with a concentration of 90 vol% and a flow rate of 4 m / s is heated to 1700°C by passing through a high-temperature carbon component for 0.6 s to obtain high-temperature hydrogen.

[0084] Application Example 6

[0085] The high-temperature hydrogen prepared in Example 6 was hydrogenated with calcite with a particle size of 0.7 mm at 900°C for 8 minutes. The ratio of the mass of calcite to the volume of high-temperature hydrogen was 1 g:2 L. Solid product calcium oxide was obtained. The yield of carbon monoxide in the gas product was 84%, and the yield of carbon dioxide was 16%.

[0086] Example 7

[0087] The method for preparing high temperature hydrogen is as follows:

[0088] (1) Induction heating the carbon component to 1800° C. in an alternating magnetic field at a frequency of 400 kHz to obtain a high-temperature carbon component; wherein the high-temperature carbon component is made of coke;

[0089] (2) Hydrogen with a concentration of 99.9 vol% and a flow rate of 4 m / s is heated to 1500°C by passing through a high-temperature carbon component for 1 second to obtain high-temperature hydrogen.

[0090] Application Example 7

[0091] The high-temperature hydrogen prepared in Example 7 was hydrogenated with dolomite with a particle size of 0.5 mm at 700°C for 15 minutes. The ratio of the mass of dolomite to the volume of the high-temperature hydrogen was 1 g:2 L. Solid product calcium oxide was obtained. The yield of carbon monoxide in the gas product was 89%, and the yield of carbon dioxide was 11%.

[0092] Example 8

[0093] The method for preparing high temperature hydrogen is as follows:

[0094] (1) Induction heating the carbon component to 2800° C. in an alternating magnetic field at a frequency of 800 kHz to obtain a high-temperature carbon component; wherein the material of the high-temperature carbon component is graphite;

[0095] (2) Hydrogen with a concentration of 50 vol% and a flow rate of 2 m / s is heated to 2000°C by passing through a high-temperature carbon component for 0.5 s to obtain high-temperature hydrogen.

[0096] Application Example 8

[0097] The high-temperature hydrogen prepared in Example 8 was hydrogenated with limestone with a particle size of 0.1 mm at 1500°C for 1 min. The ratio of the mass of the limestone to the volume of the high-temperature hydrogen was 1 g:1 L. Solid product calcium oxide was obtained. The yield of carbon monoxide in the gas product was 78%, and the yield of carbon dioxide was 22%.

[0098] It can be seen from the above embodiments that the temperature of the high-temperature hydrogen provided by the present invention reaches 1500-2000°C.

[0099] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing high-temperature hydrogen, comprising: High-temperature carbon components are used to heat hydrogen to obtain high-temperature hydrogen; The temperature of the high temperature carbon component is 1700-3000°C.

2. The preparation method according to claim 1, characterized in that: The material of the high temperature carbon component includes coke, needle coke or graphite.

3. The preparation method according to claim 1, characterized in that: The high temperature carbon component is heated by electromagnetic induction heating.

4. The preparation method according to claim 1, characterized in that: The concentration of the hydrogen is 50.0-99.9 vol%.

5. The preparation method according to claim 1, characterized in that: The heating time is 0.01 to 1 second.

6. High-temperature hydrogen prepared by the preparation method according to any one of claims 1 to 5.

7. The high temperature hydrogen according to claim 6, characterized in that: The temperature of the high-temperature hydrogen is 1500-2000°C.

8. Use of the high temperature hydrogen as claimed in claim 6 or 7 as a heat carrier and reducing agent for reducing metal carbonates.

9. The use according to claim 8, characterized in that: The application of the high temperature hydrogen as a reduction heat carrier and reducing agent for metal carbonates includes: The high temperature hydrogen is reacted with the metal carbonate to obtain metal oxides, carbon dioxide and carbon monoxide.

10. The use according to claim 9, characterized in that: The temperature of the hydrogenation reaction is 600-1500° C., and the time of the hydrogenation reaction is 1-15 minutes.